Azomethine copper complex dyes and process for their preparation

ABSTRACT

Copper complexes of azomethine dyestuffs of the formula   WHEREIN A is   R is alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, phenyl, benzyl, phenylethyl, styryl or phenylamino unsubstituted or substituted by chloro, bromo, alkyl of 1 to 4 carbon atoms, or alkoxy of 1 to 4 carbon atoms, X, Y, Z1 and Z2 is hydrogen, chloro, bromo, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, or nitro. The dyestuffs can be used especially for pigmenting high molecular organic material.

United States Patent 1 Hari et al.

1 1 June 24, 1975 l l AZOMETHINE COPPER COMPLEX DYES AND PROCESS FOR THEIR PREPARATION [75] Inventors: Stefan Harri, Allschwil; Karl Ronco,

Riehen, both of Switzerland [73] Assignee: Ciba-Geigy Corporation, Ardsley,

221 Filed: Dec. 112,11972 21 Appl.l lo.:314,283

[30] Foreign Application Priority Data Dec. 13, 1971 Switzerland 18146/71 [52] US. Cl. 260/438.l; 260/39 P; 260/40 R;

260/4221; 260/270 R; 260/310; 260/329 MF; 260/3322 R; 260/3461 M; 260/429 C Primary Exuminer-Helen M. S. Sneed AIIUI'HL), Agent, or F1'rm\/incent J. Cavalieri [57] ABSTRACT Copper complexes of azomethine dyestuffs of the formula wherein A is R is alkyl of l to 4 carbon atoms, alkoxy of l to 4 carbon atoms, phenyl, benzyl, phenylethyl, styryl or phenylamino unsubstituted or substituted by chloro, bromo, alkyl of l to 4 carbon atoms, or alkoxy of l to 4 carbon atoms, X, Y, Z and Z is hydrogen, chloro, bromo, alkyl of 1 to 4 carbon atoms, alkoxy of l to 4 carbon atoms, or nitro.

The dyestuffs can be used especially for pigmenting high molecular organic material.

5 Claims, No Drawings AZOMETHINE COPPER COMPLEX DYES AND PROCESS FOR THEIR PREPARA'lllUN It has been found that new valuable copper complexes of azomethine dyestuffs of the formula H ll x C=N Cu NHCOR wherein A denotes a carbocyclic or heterocyclic aromatic radical in which the methine group and the O- atom are in the o-position to one another, R denotes an optionally substituted alkyl, alkenyl, alkoxy, aralkyl, aralkenyl or arylamino group or a heterocyclic radical, are obtained if a Schiffs base of the formula A I NHCOR Ol-l R Y wherein A, R, X and Y have the indicated meaning and R denotes a hydrogen atom or an alkyl group, is reacted with a copper-donating agent.

Compounds of particular interest are those of the formula Z CH X Cu NacoR 0 o 2 wherein R, denotes an alkyl or alkoxy group containing l-4 C atoms, a benzyl, phenylethyl, styryl or phenylamino group optionally substituted by halogen atoms or alkyl or alkoxy groups containing 1-4 C atoms, or a heterocyclic radical and X, and Y, and Z, and Z denotes hydrogen or halogen atoms, alkyl or alkoxy groups containing 1 to 4 carbon atoms, or nitro groups.

R, for example denotes a methyl, ethyl, propyl, methoxy or ethoxy group.

l-urther preferred compounds are those of the formula NllC OR 2 wherein X, and Y, have the indicated meaning and R denotes an alkyl or alkoxy group containing l-4 C atoms, a phenyl, benzyl, phenylethyl, styryl or phenylamino group which is optionally substituted by halogen atoms or alkyl or alkoxy groups containing l-4 C atoms. or a heterocyclic radical.

The Schiffs bases which serve as starting substances preferably correspond to the formula Nl-lC OR 2 wherein R,, R X,, Y,, Z, and Z have the indicated meaning and R denotes an alkyl group containing 1 to 4 carbon atoms.

The Schiffs bases are obtained according to known processes by condensation of a carbocyclic or heterocyclic aromatic o-hydroxy-aldehyde with an amine of the formula NHC OR Since the o-aminophenols are compounds which are sensitive to oxidation it is more advantageous to use the corresponding o-aminophenol ethers, especially the l-amino-2-methoxybenzenes, as starting substances.

The following o-hydroxy-aldehydes may be mentioned examples: Z-hydroxybenzaldehyde, 4-chloro- Z-hydroxybenzaldehyde, 5-chloro-2- hydroxybenzaldehyde, 3-nitro-2- hydroxybenzaldehyde, 5-nitro-2 hydroxybenzaldehyde, 3,5-dichlor0-2- hydroxybenzaldehyde, 3 ,5-dibromo-2- S-phenylazo-Z- l-amino-2-methoxy-5 2 ,4'-dichlorobenzoylamino l-amino-2-methoXy-4benzoylaminobenzene, l-amino- 2-methoxy-4-(o-chlorobenzoylamino)-benzene, lamino2-methoxy-4-(p-chlorobenzoylamino)-benzene, l-amino-2-methoxy-4-(2,4 dichlorobenzoylamino)- benzene, l-amino-2-methoxy-4-(o-methylbenzoylamino)-benzene, l-amino-2-methoxy-4-(p methylbenzoylamino)-benzene, methoxybenzoylamino)-benzene, l-amino-2-meth0xy' o-methylbenzoylamino )-benzene, l-amino-Z- methoxy-S-(p-methylbenzoylamino benzen e, lamino-2-methoxy-5-(o-methoxybenzoyl-amino)- benzene, l-amino-2-methoxy-5 (p-methoxybenzoylamino)-benzene, l-amino-2-methoxy-3- acetylaminobenzene, l-amino-2-methoxy-3- benzoylaminobenzene, l-amino-2-methoxy-6- acetylamino-benzene, l-amino-2-methoxy-6- benzoylaminobenzene, l-amino-2-methoxy-5-methoxycarbonylaminobenzene, acetylaminobenzene, propionylamino-benzene, benzoylaminobenzene, 3-amino-4-methoxy-carbanilic acid benzyl ester, 3-amino-4-methoxy-carbanilide, lamino- 2,5-dimethoxy-4-( o-chlorobenzoylamino)- benzene, 1-amino-2,5-dimethoxy-4-( pchlorobenzoylamino )-benzene, l-amino-2,5- dimethoxy-4-(2,4-dichlorobenzoylamino)-benzene, l-amino-2,5-dimethoxy-4-( o-methylbenzoylamino benzene, l-amino-2,5-dimethoxy-4-( p-methylbenzoylamino )-benzene, l-amino-2,5-dimethoxy-3- acetylarninobenzene, l-amino-2,5-dimethoxy-3- benzoylaminobenzene, 1-amino-2-methoxy-5-methyl- 4-acetylaminobenzene, 1-amino-2-methoxy-5-methyl- 4-propionylaminobenzene, l-amino-Z-methoxy-S- methyl-4-benzoylaminobenzene, l-amino-2-methoxy- 5-methyl-4-( o-chlorobenzoylamino )-benzene, lamino-Z-methoxy-S-methyl-4-(pchlorobenzoylamino)-benzene, l-amino-Z-methoxy-S- methyl-4-( 2 ,4-dichlorobenzoylamino)-benzene, 1- amino-Z-methoxy- 5-methyl-4-(o-methylben- 'zoylamino)-benzene, l-amino-2-methoxy-5-methyl-4- (p-methylbenzoylamino )-benzene, l-amino-2- methoxy-S-methyl-4-(o-methoxybenzoylamino)- benzene, l-amino-2-methoxy-5-methyl-4-(2- thienylamino)-benzene, l-amino-2-methoxy-5-methyl- 4-(2-furoylamino)-benzene, l-amino-2-methoxy-5- chloro-4-acetylaminobenzene, l-amino-2-methoxy-5- chloro-4-propionylaminobenzene, l-amino-2- methoxy-S-chloro-4-benzoylaminobenzene, l-amino- 2-methoxy-5-chloro-4-(o-chlorobenzoylamino)- benzene, l-amino-2-methoxy-5-chloro-4-(pchlorobenzoylamino)-benzene, l-amino-Z-methoxy-S- chloro-4-( 2 ,4'-dichlorobenzoylamino )-benzene, lamino-2-methoxy-5-chloro-4-(o-methylbenzoylamino)-benzene, l-amino-2-methoxy-5-chloro-4- (p-methylbenzoylamino )-benzene, l-amino-2- methoxy-5-chloro-4-(o-methoxybenzoylamino)- benzene, l;amino-2-methoxy-5-chloro-4-( 2'- thienylamino)- benzene, 1-amino-2-methoxy-5-chloro- 4-(2-furoylamino)-benzene, l-amino-2-methoxy-5- nitro-4-acetylaminobenzene, l-amino-2-methoxy-5-' nitro-4- benzoylaminobenzene, l-amino-Z-methoxy-S- nitro-4-(o-chlorobenzoylamino)-benzene, l-amino- 2,S-diethoxy-4-acetylaminobenzene, l-amino-2,5-

l-amino-2,5-dimethoxy-4- l-amino-2,5-dimethoxy-4- l-amino-2,5-dimethoxy-4- diethoxy-fl-l 2',4'-dichlorobenzoylamino )-bcnzenc.

. 4 diethoxy-4-ben2oylamino'beniencl 'l-amino-Zjamino-2-methoxy-4 -phenacetylaminobenzene, amino-Z-methoxyS-phenacctylaminobenzenc, amino-2-methoxy-3-phenacctylaminobenzcnc. amino-2,5-dimethoxy-4-phenacetylaminobenzene, amino-Z-methoxy-S-methyl-4- phenacetylaminobenzene. l-amino-2 methoxy-5- chloro-4-phenacetylaminobcnzene, l-amino-Z- methoxy-S-naphthylacetylaminobenzene, l-amino-2- methoxy-S-phenoxyacetylaminobenzene, l-amino-Z -methoxy-5-(p-chlorophenoxyacetylamino)-benzcne, l-amino-2-methoxy-5-phenylthioacetylaminobenzene, l-amino-2-methoxy 4-phenylthioacetylaminobenzene, l-amino-2,5-dimethoxy-4-phenylthioacetylaminobenzene, l-amino-2-methoxy-5-methyl-4-phenylthioacetylaminobenzene, l-amino-2-methoxy-5-chloro-4- phenylthioacetylaminobenzene, and l-amino-2,5- diethoxy-4-(2,4'-dichlorophenylthioacetylamino)- benzene.

The reaction of the aldehydes with the amines is appropriately carried out by heating in an organic solvent.

As cooper-donating agents, the salts of divalent copper, for example copper chloride, copper sulphate and especially copper acetate, are preferably used. If starting from the o-hydroxy-o-alkoxy-azomethines, a dealkylation takes place simultaneously with the coppering. In that case the reaction appropriately takes place in an organic solvent, for example glycol monomethyl ether or glycol monoethyl ether, dimethylformamide or N- methylpyrrolidone, at temperatures above l00 preferably between and C.

Because of their insolubility in the reaction medium, the copper complexes can be isolated by filtration.

The new dyestuffs are valuable pigments which can be used, in a finely divided form, for pigmenting high molecular organic material, for example cellulose ethers and cellulose esters such as ethylcellulose, nitrocellulose, cellulose acetate, cellulose butyrate, polyamides and polyurethanes or polyesters, natural resins or synthetic resins, such as polymerisation resins or condensation resins, for example aminoplasts, especially urea-formaldehyde and melamine-formaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyolefines, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, polyacrylic acid esters, rubber, casein, silicone and silicone resins, individually or as mixtures.

It does not matter whether the high molecular compounds mentioned are in the form of plastic masses or melts or in the form of spinning solutions, lacquers, paints or printing inks. Depending on the end use it proves advantageous to use the new pigments as toners or in the form of preparations.

The new dyestuffs are distinguished by outstanding fastness to light, especially in lacquers and on intaglio prints, and by excellent fastness to migration, overlacquering and weathering.

In the examples which follow the parts, unless otherwise indicated, denote parts by weight and the percentages denote percentages by weight.

EXAMPLE 1 118.0 parts and then allowed to cool to 85C. The mixture is now diluted with 10 parts by volume of alcoholwater 1:1 and thereafter with 100 parts by volume of water. and cooled to 25C, and the yellow precipitate formed is filtered off. The residue is washed with alcohol-water (1:1) and with distilled water and is dried. The yellow crystal powder thus obtained (21.2 parts or 75% or theory) melts at 166 to 167C.

8.5 parts of this product and 6.0 parts ofcopper-ll acetate monohydrate in 100 parts by volume of glycol monomethyl ether-dimethylformamide 1:1 are heated to 135C whilst stirring vigorously, stirred for 2.5 hours at this temperature. allowed to cool to 50C and filtered off warm. The filter residue is successively washed with a 1:1 mixture of glycol monomethyl ether and dimethylformamide. methanol and distilled water and again with methanol and is dried. The resulting pig- (70% of theory) of a yellow powder of melting point 147 to 148C are obtained. 2. 4-Acetylamino-2amino-anisole 21 parts of 4-acetylamino-2-nitro-anisole are suspended in 300 parts by volume of absolute alcohol and hydrogenated with hydrogen and Raney nickel for 13 hours at 2550C. The resulting solution is freed ofthe Raney nickel by filtration and diluted with 4.000 parts by volume of petroleum ether and the precipitate formed is filtered off and dried in vacuo. It is a grey crystal powder which melts at 102 to 103C. The yield is 15.8 parts (88% of theory).

The table which follows lists further pigments which are obtained in the indicated manner. Column I indicates the base used instead of 4-acetylamino-2-aminoanisole and column 11 indicates the colour shade of a polyvinyl chloride film dyed with the dyestuff.

Example 1 11 2 4-Propionylamino-2-amino-anisole Green-yellow 3 4-ButyrylaminoZ-arninoanisole Greenyellow 4 4-Acryloylamino-2amino-anisole Green-yellow 5 4-Stearoylamino-2-amino-anisole Green-yellow 6 4-Phenacetylamino-2-amino-anisolc Green-yellow 7 4-Phcnoxyacetylamino-2-amino-anisole Green-yellow 8 4-(4-Chlorophenoxyacetylamino)-2-amino-anisole Green-yellow 9 4 (2..5-Dichlorophenoxyacetylamino)-2 amino-anisole Yellow 10 4-(3'-Phenyl-propionylamino)-2-amino-anisolc Green-yellow l 1 4-Cinnamoylamino2 arnino-anisole Greenyel1ow 12 4'phcnylmercaptoacetylamino-2-amino-anisolc Green-yellow 13 4-(3'-Chloro-4-methyl-phenylrnercaptoacetylamino)-2-amino-anisole Green-yellow 14 4-(4'-Chloro-2'-methyl-phenylmercaptoacctylamino)-2-amino-anisole Green-yellow 15 3-Amino-4-methoXy-carbanilic acid benzyl ester Green-yellow l6 5-Cinnamoylamino-2-amino-anisole Yellow 17 5-Cinnamoylamino-2-amino-4chloro-anisole Yellow 18 4-( wThenoylamino 2 amino-anisole Green-yellow ment is a light green powder and corresponds to the formula 110C CH A I benzene and 31 parts by volume of pyridine and 18.8 parts of acetyl chloride are added. In the course thereof. the temperature rises to 60C. The black solution is stirred for 3 hours at 95C and allowed to cool to room temperature. The precipitate which hereupon forms is filtered off, washed with petroleum ether. alcohol-water (1:1) and hot water and dried. 29.4 parts EXAMPLE 19 7.8 parts of 4-cinnamoylamino-2-amino-anisole and 5 parts of 2-hydroxy-1-naphthaldehyde in parts by volume of glycol monomethyl ether are heated to 120C. stirred for 2 hours at this temperature and cooled. The resulting ochre-yellow precipitate is filtered off, washed with 300 parts by volume of alcohol and 300 parts by volume of distilled water and dried. 9.5 parts (77 percent of theory) of an ochre-yellow powder of melting point 245 to 247C are obtained.

9.4 parts of this product and 4.4 parts of cooper-l1 acetate monohydrate in 80 parts by volume of glycol monomethyl ether-dimethylformamide (1:1) are heated to 132C with vigorous stirring, stirred for 2.5 hours at this temperature and filtered hot. The filter reidue is successively washed with dimethylformamide, methanol and distilled water and again with methanol and is dried. The resulting pigment is a khaki-coloured powder and corresponds to the formula The yield is 7.2 parts (70% of theory). The new copper complex dyes polyvinyl chloride in yellow shades of very good fastness to light and to migration.

EXAMPLE 20 9.0 parts of 4-acetylamino-2-aminoanisole and 10.1 parts of l-phenyl-3-methyl-4-formyl-pyrazolone-(5) are reacted in 100 parts.by volume of glycol monomethyl ether analogously to Example 1. 17.1 parts (94 percent of theory) of Schiffs base are obtained as a yellow powder of melting point 208 to 210C.

at 95Cand allowedto cool to roomtemperature whilst stirring The precipitate-which hcreupon forms is.fil- .tered off, washed with petroleumether alcohol-water 1:1) and hot water and dried. 49.2 parts (90 percent 3-carboxylic acid 4-Benzoylamino-2-amino-anisole can be manufactured as follows: 1. 4-Benzoylamino-2rnitro-anisole 38.6 parts of 87% strength of 4-amino-2-nitro-anisole are dissolved in 350 parts by volume of chlorobenzene and 31 parts by volume of pyridine and 33.5 parts of benzoyl chloride are'added. Hereupon the temperature rises to 55C. The black solution is stirred for 3 hours Parts of this Product and P of pp of theory) of a khaki-coloured crystal powder of meltacetate monohydrate are coppered under demethylati i t 141 to 143C are b i d ingconditions in 100 parts by volume of a mixture con- 2, 4 B 1 i 2 1 1 slstlng of glycol monomethyl ether and dlmethylfolm- 40.8 parts of 4-benzoylamino-2-nitrtH1nisole are susamide in the Volume ratio of analogously Exam- -pended in 400 parts by volume of absolute alcohol and p h resulting Pigment of the formula 10 hydrogenatedwith hydrogen and Raney nickel for 4 NHOCCH hours at 25C. The resulting solution is freed of the 3 Raney nickel by filtration and diluted with 1.400 parts by volume of water and the precipitate formed'is filtered off and dried in vacuo. The product is a grey powl5 der which melts at 135to 136C. The yield is 30.9

parts (85% of theory).

EXAMPLE 27 10 g of titanium dioxide and 2 g of the pigment manudyes polyvinyl chloride in very greenish-tinged yellow factured according to Example 1 were ground for 48 Shadgs of good fasmess to light and to migration hours in a ball mill with 88 g of a mixture of 26.4 g of EXAMPLE 21 coconut alkyd resin, 24.0 g of melamine-formaldehyde j resin (50% solids content), 8.8 g of ethylene glycol 9 parts of 2-amino-4-acetylammo-amsole, 9.6 parts 25 monomethyl ether and 2&8 g of xy|ene of 3,5-dichlorosalicylaldehyde and 10 parts of copper- A lacquer film was applied to cardboard and Stoved ll acetate monohydrate in 160 parts by volume of a for minutes at 120C mixture consistlngPf glycol monomethyl ether and l The fastness to overlacquering was determined by methylformamide in the volume ratio of 1:1 are heated overlacquering the film on the cardboard with a white to 130C vlgorous Surfing l i' to 9 to 30 lacquer which contained 20 percent of titanium dioxide I 10 C and filtered hot. The filter residue-is successively and again Stoving for 30 minutes at 120C The result Washed 'wlth dlmethylform?mld? methanol, and hot ing colouration of the white film was then rated. The water and dned' The resultmg p'gmem 1S a hght green heat stability was determined after again stoving sam- Powder and corresponds to the formula ples of the lacquer films for 30 minutes at 120C and 1;1 15 minutes at 180C. The fastness to light was deter- NllCOCll mined by exposing the samples to the light of a xenon C1 C==N 3 are lamp and comparing to the Blue Wood Scale [British Standard 1006 (1961)]. It was found that the fast- 40 ness to light, the heat stability and the fastness to over- I O-Cu- O lacquering are excellent. Cl The yield is 12.3 parts. The new copper complex dyes EXAMPLE 28 polyvinyl chloride in yellow shades of very good fast- The dihydroxyazomethine-copper-Il complex acness to light and to migration. cording to Example 1 was incorporated into an emul- The table which follows lists further dyestuffs which sion paint. are obtained in the indicated manner. Column 1 indi- A paste consisting of 20 parts of the pigment, 80 cates' the aldehyde, column I] the base used instead of parts of water and 2.5 parts of sodium dinaphthylme- I 4-acetylamino-2-amino-anisole and column 111 the colthanedisulphonate was formed and was ground for 48 our shade of the polyvinyl chloride film dyed with the hours with parts of coarse quartz sand. The sand was copper complex. removed by sieving. 0.3 part of thispaste was mixed Example 1 ll 22 Salicylalclehyde 2-Amino-4-acetyl-amino-anisole Greenish-tinged yellow 23 2-Hydroxyl -naphthaldehyde 2-Amino-4-acetyl-amino-anisole Yellow 24 2-Amino-4-benzoyl-amino-amsole Yellow 25 l 2-Amino-4-methyl-5-benzoylamino-anisolc Yellow 26 l-F0rmyl-2-hydroxynaphthalene- 2-Amino-4-benzoyl-amino-anisole Yellow with 30 parts of polyvinyl-acetate emulsion and stirred XA PL 29 15 parts of the product according to Example 1 were stirred into 500 parts of dimethylformamide until a uni- 9 10 form dispersion was obtained. This dispersion was di- 1 to 4 carbon atoms, alkoxy of l to 4 carbon atoms, luted with 8.000 parts of dimethylformamide. 1.500 or nitro. parts of polyacrylonitrilc powder were added to this 2. A compound according to claim ll having the for dispersion and the mixture was stirred at high speed mula until a uniform lacquer was obtained. After removing 5 the air, the lacquer was suitable for the manufacture of films and filaments since the pigment was present in a NHOCCH CH :N highly dispersed form and no large particles could be 3 seen. Films 0.05 cm (20/l,000 inch) thick were spread l l on glass and immediately dried for 15 minutes at 0 cu O 120C. Bright, strong, transparent, yellow films having excellent fastness to light were thus obtained.

EXAMPLE 30 65 parts of stabilised polyvinyl chloride, 35 parts of dioctyl phthalate and 02 part of the dyestuff obtained according to Example 1. paragraph 2 were stirred together and then milled on a two-roll calender for 7 minutes at 140C. A yellow-coloured film of very good fast- CH w N NHCOCH2CH2CH3 ness to light and to migration was obtained.

We claim:

3. A compound according to claim ll having the formula o cu 0 l. A copper complex of an azomethine dyestuff of the formula X 4. A compound according to claim 11 having the for mula /c= NHCOR l A\ Cl C -N NHCOCH Y 3 Q Cu O 3Q I i Q) 0- cuo wherein A is 5. A compound according to claim ll having the foror mula 4O 2 CH /N CH3 1/ I fie R is alkyl of l to 4 carbon atoms, alkoxy ofl to 4 car- 0 bon atoms, phenyl, benzyl, phenylethyl, styryl or phenylamino unsubstituted for substituted by chloro, bromo, alkyl of l to 4 carbon atoms, or alkoxy of l to 4 carbon atoms, X. Y, Z and Z is hydrogen, chloro, bromo, alkyl of 

1. A COPPER COMPLEX OF AN AZOMETHINE DYESTUFF OF THE FORMULA
 2. A compound according to claim 1 having the formula
 3. A compound according to claim 1 having the formula
 4. A compound according to claim 1 having the formula
 5. A compound according to claim 1 having the formula 